JPH02275941A - Direct positive photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the direct positive photographic sensitive material which forms images having the low min. image density and the high max. image density by incorporating >=5mol% silver chloride into internal latent image type silver halide particles and perfectly uniformizing the distribution of the silver chloride in at least a part of the region contg. the silver chloride in the particles. CONSTITUTION:The internal latent image type silver halide particles contain >=5mol% silver chloride and the distribution of the silver chloride in at least a part of the region contg. the silver chloride in the particles is perfectly uniformized. the silver ions and halide ions which successively form the particles are supplied in the form of the fine silver halide particles having a halide compsn. to grow the particles, by which the perfectly uniform distribution of the silver chloride is obtd. The advantages in containing the silver chloride are fully effectively utilized to incease the developing rate and fixing rate and to lower the min. density with the silver halide particles having the perfectly uniform silver chloride distribution. The direct positive images having the high max. image density and the low min. image density in combination are obtd. in this way.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a silver halide photographic material, and more particularly to a direct positive photographic material.

[Conventional technology]

Photographic methods that provide direct positive images without the need for reversal processing steps or negative film are well known.

Excluding special methods, the methods used to create positive images using conventionally known direct positive silver halide photographic materials can be mainly divided into two types, considering their practical usefulness. can.

One type uses a partially fogged silver halide emulsion and uses solarization or the Burschel effect to destroy fog nuclei (latent images) in exposed areas, thereby obtaining a positive image directly after development. It is.

The other type uses an unfogged internal latent image type silver halide emulsion and directly obtains a positive image by performing surface development after or while performing fogging treatment after image exposure. .

The above-mentioned internal latent image type silver halide photographic emulsion is a type of silver halide photographic emulsion that has photosensitive nuclei mainly inside the silver halide grains and a latent image is mainly formed inside the grains upon exposure. means.

As mentioned above, as a means for selectively generating fog nuclei, a method of applying a second exposure to the entire surface of the photosensitive layer (for example, British Patent No. 1,151,3
63) and a nucleating agent (nu
creating agent) is known. This latter method is discussed, for example, in Research Disclosure.
Closure) Vol. 151 It, 151.62 (
No. 76-78 (issued November 1976).

Compared to the former type of method, this latter type of method has - higher sensitivity for boat fishing (and is suitable for applications requiring high sensitivity).

Various techniques are known to date in this technical field. For example, U.S. Patent Nos. 2.592250, 2.466.957, 2.4.97,875,
2,588,982, 3.3], 7,322
No. 3.76L 266, No. 3,761,2
No. 76, No. 3,796 577 and British Patent No. 1
．． ．． No. 151,363, same No. 1. ．． No. 150.553 (
No. 1.011062) The main ones are those described in each specification, etc.

By using these known methods, it is possible to produce photographic materials with relatively high sensitivity as direct positive type materials.

For details on the direct positive image formation mechanism, see
T, 11. The Theory of the Photographic Process by James
of the Photograpl+ic r'ro
cess) 4th edition, Chapter 7, pages 182 to 193, and US Pat. No. 3,761,276.

In other words, fog nuclei are selectively generated only on the surface of the silver halide grains in unexposed areas due to the surface desensitization effect caused by the so-called internal latent image generated inside the silver halide by the initial imagewise exposure. It is believed that a photographic image (direct positive image) is then formed in the unexposed area by subjecting it to a normal so-called surface development process.

[Problem to be solved by the invention]

In direct positive image formation using such optical or chemical scattering methods, the development speed is slower and processing time is longer than in the case of a normal negative type. Methods have been used to shorten the processing time by increasing H and/or liquid temperature. However, in general the pH
There is a problem that the minimum image density of the direct positive image obtained increases when the value is high. Furthermore, under high pH conditions, the developing agent is likely to deteriorate due to air oxidation, and there is a problem in that the imaging activity thereof is significantly reduced.

In addition to increasing the pH, there are other ways to increase the development speed for direct positive image formation, such as using hydroquinone derivatives (US Pat. No. 3,227,552) and using mercapto compounds having carboxylic acid groups or sulfonic acid groups. However, the effect of using these compounds is small, and it is difficult to directly increase the minimum density of a positive image without increasing it. No technology has been found that can do this. Especially low p
There is a need for a technique that can provide a sufficient maximum image density even when processed with a H developer.

On the other hand, silver chloride is more soluble than other photographically useful silver halides. Therefore, it is difficult to directly form a positive photographic material using silver halide containing silver chloride.
This is extremely advantageous for rapid processing. However, this case also has the disadvantage that the minimum image density does not increase. In order to improve this drawback, a technique for controlling the crystal habit of particles is described in Japanese Patent Application No. 62-280467, but it is still not sufficient.

In negative-working silver halide emulsions, several methods have been proposed to solve the drawback that silver halide grains containing silver chloride tend to fog. For example, as described in JP-A-48-51627 and JP-B-49-46932, a method in which a sensitizing dye is added to a silver halide emulsion and then a water-soluble bromide ion or iodide ion is added; No. 58-1.08533, JP-A-60-2
As described in No. 22845, etc., bromide ions and silver ions are added simultaneously to silver halide grains with a high silver chloride content to form a layer of silver bromide of 60 mol % or more on the surface of the grains. Method: Similarly, a method in which a layer of silver bromide of 10 mol % to 50 mol % is provided on the entire surface or part of the surface of the grain; Japanese Patent Publication No. 50-36978, Japanese Patent Publication No. 58
-24.772υ, U.S. Patent No. 4471050 and 0LS
By adding bromide ions to silver halide with a high silver chloride content, or by simultaneously adding bromide ions and silver ions, halogen exchange is performed to obtain core-shell double structure particles or Methods for producing particles with a multiphase structure such as bonded structure particles are known.

The content described in these patents is to vary the silver bromide content in each silver chlorobromide grain depending on the location (particularly on the inside or outside of the grain, or on the surface of the grain), thereby making it more concentrated. The aim is to obtain good photographic characteristics.

However, even when these methods are applied directly to positive photographic materials, satisfactory results have not yet been obtained.

Accordingly, a second object of the present invention is to provide a direct-positive photographic material that provides a direct-positive image having a low minimum image density and a high maximum image density.

A second object of the present invention is to provide a direct positive photographic material that can provide a direct positive image having both a low minimum image density and a high maximum image density even by rapid processing.

[Failure to solve the problem]

The above object of the present invention is to provide a direct positive photographic light-sensitive material having at least one photographic emulsion layer containing internal latent image type silver halide grains which have not been fogged in advance, wherein the internal latent image type silver halide grains contain 5 mol of internal latent image type silver halide grains. Contains more than % silver chloride,
This is achieved by a direct positive photographic light-sensitive material characterized in that the distribution of silver chloride is completely uniform in at least some regions containing silver chloride in the grains.

The internal latent image type silver halide grains which are not fogged in advance and are used in the present invention will be explained.

First, the "completely uniform silver chloride distribution" referred to here will be explained.

The term "completely uniform silver chloride distribution" used herein refers to a more microscopic distribution, which is completely different from the silver chloride distribution that has been handled up to now. As a means of measuring silver chloride distribution (or silver bromide distribution) in silver chlorobromide grains, an analytical electron microscope (Analytical Electron Mic) is used.
roscopy) is often used.

In order, King (mon, eight, King), o let (
M, l+.

Lorretto), Mattanahan (T, J, Maj.
crnaBl+an) and heli-(F, J, Berry
) Study of iodine distribution using analytical electron microscopy
Microscopy), Progress in Scientific Principles of Imaging Systems, International Combinations of Photocraffing Science Cologne (KBln), 1986, measured the distribution of silver iodide in silver iodobromide tabular grains.

The size of the electron beam irradiation probe used at that time was 50 people, but in reality, the electron beam spreads due to the elastic scattering of electrons, and the diameter of the electron beam spot irradiated on the sample surface was approximately 300 Å or more. It is stated that the

Therefore, this method cannot measure a finer silver chloride distribution. In JP-A-58-113927, the silver iodide distribution in ζζ iodobromide powder particles was measured using the same method, but the electron beam spot used was 0.2t.
! Met.

Therefore, depending on these measurement methods, more microscopic (30
It is impossible to clarify the distribution of silver chloride (locational variations on the order of 0 or less).

This microscopic silver chloride distribution is, for example, Hamiltonian (
J, F, llamilton), Photography Inc. i Neuens and Engineering Volume 11,
1967, p., p. 57, Takeshi Shiozawa, Photographic Society of Japan
It can be observed by a direct method using a transmission electron microscope at low temperature as described in Vol. 35, No. 4, 1972, p. 213. That is, silver halide grains were taken out under safe light to avoid printing out the emulsion grains, placed on a mesh for electron microscopy, and then exposed to +
iff(g(printout) Observe by transmission method with the sample cooled with helium.

Here, the higher the accelerating voltage of the electron microscope, the clearer the transmitted image can be obtained, but for particle thicknesses up to 0.23 μm, 200 k
7000k for grain thickness greater than voltX
VO1t is good. The higher the accelerating voltage, the greater the damage to particles caused by the irradiated electron beam, so it is preferable to cool the sample with liquid helium rather than liquid nitrogen.

The imaging magnification can be changed as appropriate depending on the particle size of the sample, and is from -10,000 times to 1,000 times.

When a transmission electron micrograph of silver chlorobromide tabular grains is taken in this manner, a very fine tree-ring-like striped pattern is observed in the silver chlorobromide phase.

This situation is described in Japanese Patent Application No. Sho z3-/ri 4#6/.

It can be seen that the spacing between these striped patterns is on the order of 1 or <1ooX or less, indicating very microscopic non-uniformity. It can be clarified by various methods that this extremely irregular striped pattern indicates non-uniformity of silver chloride distribution, but more directly, it is possible to clarify that this very irregular striped pattern indicates non-uniformity of silver chloride distribution.
Annealing (annealing) under conditions that allow movement within the silver halide crystal
This can be clearly concluded from the fact that this striped pattern completely disappears when the striped pattern is removed (e.g., at 230° C. for 13 hours).

The ring-like striped pattern showing the non-uniformity of silver iodide distribution in tabular silver iodobromide can be seen in the transmission electron micrograph disclosed in JP-A-31-1983-27 cited above. is clearly observed, and is also clearly shown in the transmission electron micrograph in the study by King et al. cited earlier. Furthermore, Japanese Patent Application No. 3-7G3.2 discloses transmission electron micrographs showing the non-uniformity of silver iodide distribution in tabular silver iodobromide grains having a silver iodide content of 10 moles.

There have been no cases in which the tree-ring-like striped pattern described above, which indicates microscopically uneven distribution of silver chloride, in tabular silver chloride grains containing silver chloride, such as silver chlorobromide tabular grains, has been observed. . Due to these facts, silver chlorobromide grains that have been prepared so far to obtain a substantially uniform halogen distribution have been found to have very microscopically non-uniform silver chloride distribution, contrary to the intention of their manufacture. However, there is no technology disclosed for making the distribution uniform, and no method for manufacturing the same is disclosed.

As mentioned above, the silver chloride grains of the present invention having a "completely uniform silver chloride distribution" can be obtained by observing the transmitted image of the grains using a cooled transmission electron microscope. , can be clearly distinguished from conventional 7.silver halide grains. That is, the silver chloride-containing silver chloride grains of the present invention have at most one, preferably 7 microscopic lines at Oo-μm intervals due to microscopic non-uniformity of silver chloride. Books, preferably, don't exist. The lines that make up the tree-ring-like stripes that show the microscopic heterogeneity of silver chloride occur perpendicular to the direction of grain growth, and as a result, these lines extend concentrically from the center of the grain. to be distributed. For example, in the case of tabular grains, the lines constituting the ring-like striped pattern are perpendicular to the growth direction of the tabular grains, so as a result they are parallel to the edges of the grains.
In addition, the direction perpendicular to these points points toward the center of the particle, and the particles are distributed concentrically with respect to the center of the particle.

Of course, if the silver chloride content changes rapidly during grain growth, the boundary line will be observed as a line similar to that described above using the above observation method, but such a change in silver chloride content is simply It only consists of one line, and can be clearly distinguished from one consisting of multiple lines resulting from microscopic non-uniformity of silver chloride. Furthermore, such a line resulting from a change in silver chloride content can be clearly confirmed by measuring the silver chloride content on both sides of this line using the analytical electron microscope described above.

In the present invention, the line due to such a change in silver chloride content is
This line is completely different from lines originating from microscopic non-uniformity of silver chloride, and shows a ``macroscopic distribution of silver chloride''. In addition, since there is no rapid change in the silver chloride content in the case where the silver chloride content is changed substantially continuously during grain growth, the line showing the macroscopic change in the silver chloride content is observed. Therefore, if there are at least three lines at intervals of 2 μm, it means that there is microscopic non-uniformity in the silver iodide content.
/4t- That's it.

Thus, the silver chloride grains of the present invention with completely uniform silver chloride distribution have microscopic particles at intervals of 0.2 μm in the direction perpendicular to the line at the transparent edge of the grain obtained using a cooled transmission electron microscope. It is a grain having at most one line showing a silver chloride distribution, preferably 7 lines, preferably a silver halide grain having no such line, and such a grain is Occupying at least 4tO% of the total particles, preferably at least 60%, preferably at least 0% of the total particles.
These are silver halide grains.

This method of confirming microscopic halogen non-uniformity using a cooled transmission electron microscope is mainly applied to tabular silver halide grains.

On the other hand, for non-tabular silver halide grains, microscopic non-uniformity of halogen distribution can be confirmed by a method using X-ray diffraction as described below.

It is well known in the art to determine halogen composition using an X-ray diffractometer. This principle can be briefly described as follows. By measuring the Bragg angle in X-ray diffraction, the following BraggO
The lattice constant a is determined by the formula, 2d sinθ
=λh k l h k 1 λ: X-ray wavelength θhJ: Bragg angle dhk from (hkl) plane
A: < 1ikl) Interplanar spacing a: Lattice constant can be constant. By the way, T.H. J'ame
``The Theory of the F1 Graphic Process J'' by S)
the Photographic Processes
s) 1st edition Macmillan, New York (Macmi
For silver iodobromide, silver chlorobromide, and silver iodochloride, the relationship of the lattice constant a to the Rogge/composition is shown in Chapter 1 of 2009 (IllanCo, Ltd., New York). When the lattice constant (halogen composition) differs in this way, the diffraction vibration position differs. Therefore, silver halide grains with excellent uniformity of halide composition distribution and little variation in lattice constant have a narrow half-width of the diffraction profile. In this 6111-determination of the diffraction profile, the Kct line, which has high intensity and good monochromaticity, is preferably used as a radiation source. Note that since the Ko line is a double line, it is possible to obtain a single profile and determine the half-width using Rachj's method.

For the sample, powder particles obtained by removing gelatin from an emulsion may be used, or powder particles obtained by removing gelatin from an emulsion may be used, or particles obtained by removing gelatin from an emulsion may be used.

graphxc 5science) /1P71. Year + 2≠Volume''-G, C, Farnell (G, C.

Farnell), R. J., Zienkins (R. J.).

Jenkins) and Ri, R, Sorma: / (L,
R.

A coated emulsion film can be used which has been immersed in a 30% glycerin solution for 20 minutes to remove the pressure built up on the surface of the gelate/particles in the buffy coat, according to the method of J.D. Solman. In order to accurately determine the angle of the diffraction profile -/7-, a method is used in which Si powder or Naα powder with a known diffraction angle is mixed into the lamp. Furthermore, it is known that in order to accurately measure the diffraction angle and the line width of the diffraction profile, it is better to use a diffraction profile with a large diffraction angle from a high index plane. Therefore, in this patent, the Ka line of the copper target (≠, 2
The diffraction profile of the 0) surface was measured in the region of diffraction angle (one time Bragg's angle) 7/° to 77°.

In X-ray diffraction measurements, measurement accuracy is better for coated emulsion films than for powders.

By the way, the half-width of the diffraction profile of a system without distortion due to external stress, such as the sample configuration described in this patent, is:
- It is determined not only by the Rogge/composition distribution, but also includes the half-width determined by the optical system of the diffractometer and the half-width determined by the size of the crystallites (crinutarinots) in the sample. Therefore, in order to obtain the half-width due to the 7.logen composition distribution, it is necessary to subtract the contribution of the former two to the half-width. The half-width due to the optical system of the diffractometer has never been distorted.
/ and -7=no variation in constant], can be obtained as the half-width of the diffraction profile of a single crystal with a grain size of 2 tμm or more.

An example of such a sample is α-quartz with jj~t≠μm (too mesh on 3!0 mesh under).
The use of a material annealed at 0θ0C is described in Chapter 2 of the revised edition of the X-ray diffraction manual by Rigaku Denki Co., Ltd. It is also possible to use 81 grains, S1 single crystal wafers, etc. Since the half-width due to the optical system is dependent on the diffraction angle, it is necessary to find the half-width for several diffraction profiles. Extrapolation and interpolation are performed as necessary to obtain the half-value width of the optical system for the diffraction angle of the system being measured. The half-width depending on the crystallite size is described by the following equation.

β: Half width (0) due to crystallite size K: Constant (
D: Crystallite size (A) λ: X-ray wavelength (input) β: Bragg angle Half-width and crystallite obtained from the optical system from the half-width of the measured diffraction profile By subtracting the half-width due to the size of , the half-width due to the halogen composition distribution is obtained. The half-value width determined by the optical system and the half-value width determined by the crystallite size of the mixed crystal grain that we want to measure now are the same as those of the halogen composition distribution (constant lattice constant) that has the same crystallite size as the particle we are focusing on. This is equivalent to the half-width of the diffraction profile of silver oxide grains. Generally, in the absence of distortion due to external stress, the size of a particle without lattice defects (side length, diameter equivalent to an equal volume sphere, etc.) matches the size of a crystallite. Although this is not a diffractometer, but a method, the size of AgBr crystallites determined by the diffraction linewidth agrees with the particle size, as reported in the Pritish Journal on Applied Physics (
Br1tish Journal of Appl
F, W, Willets (F, W, Willets) on page 3.23 of Volume 6, 7 of iedPhysics)
) has been reported. This report uses the standard deviation of the profile rather than the half-width in the photographic method and selects /, l/:4t as the Sierra constant. In our measurement system, we use a diffraction meter (f), and use a Si single crystal to find a balance between the crystallite size and the particle size, which is calculated from the half-width obtained by subtracting the half-width due to the optical system.
We found good agreement in AgBr particles prepared by double jetting.

In other words, the half-value width due to the optical system and the half-value width due to the crystallite size of the mixed crystal emulsion grains are the half-value widths of the diffraction profiles of A g Br grains, AgJ grains, and AgI grains having the same grain size as the mixed crystal emulsion grains. Obtainable.

The half-width due to only the halogen composition distribution of mixed crystal emulsion grains is:
It is obtained by subtracting the half-width of 7% from the half-width of the measured diffraction profile of AgBr particles, AgL:i particles, and AgI particles of the same particle size as the measured diffraction profile.

Xa! of silver halide emulsion grains having a uniform microscopic halogen composition according to the present invention by the above method! The preferred half width of the diffraction profile is shown in FIG. 1 for silver chlorobromide. In FIG. 7, the uniformity of grains of each halogen composition is shown by the value obtained by subtracting the half-width of pure silver chloride or pure silver bromide of the same grain size from the half-width of X-ray diffraction of each grain. The particles of the present invention have a width at half maximum shown by curve A or less,
Preferably, it has a half-value width smaller than the half-value jIli,i shown by the uIi line B.

Silver halide grains, which have so far been called silver halide grains containing uniform silver chloride, are simply made by reacting silver nitrate with a haloken salt mixture of a constant composition (constant iodide content) using a double-jet method during grain growth. Although the macroscopic distribution of silver chloride in such particles as added to the container is certainly uniform, the microscopic distribution of silver chloride is not uniform. In the present invention, such grains are referred to as tabular grains with a "certain halogen composition" and are "uniform throughout".
j? −j Clearly distinguished from the tabular grains shown in the table below.

In the present invention, the composition of silver halide grains having a completely uniform silver chloride distribution may be any of silver chlorobromide, silver iodochloride, and silver iodochlorobromide; Silver bromide is preferred.

The position of the phase containing silver chloride within the grain may be in the center of the grain, throughout the grain, or in the outer part. Further, the number of phases in which silver chloride is present may be seven or more.

In general, a phase containing silver chloride often forms a layered structure due to the mechanism of grain growth, but it may also be a part of determination. For example, by utilizing the difference in properties between the edges and corners of particles, chloride chain pores can be formed only at the edges or only at part of the corners. Further, by forming a shell on the outside from the grain, it is also possible to produce a silver chloride grain having silver chloride at a specific point without an annular structure inside the grain.

Specifically, after nucleation, an example can be provided in which grain growth is performed using the configuration shown below.

First coating layer Second coating layer Third coating layer/ Uniform Ag
BrC1,2AgEr average-AgBrCg3 average-AgB r CI AgB rt
〃 Uni-AgBrC/! j A g B r
tt A g B rt
〃 Uneven-AgBrCg Uniform-AgBrQ!
7 Average-AgBrCg AgBr Average-AgB
rCgt heterogeneity-AgBrα 〃
〃Ta 〃Uni-
AgB r Ci AgB rlo Uniform-Agf3r (J Unequal-A g B r ct
tt strip uniformity means "completely uniform" as used in the present invention.

Further, in the case of silver iodochlorobromide, silver iodide may be contained in the above layer, and the layer containing silver iodide may be any of the first coating layer, the second coating layer, and the third coating layer.

In the present invention, the average proportion of −AgBr in one particle
The proportion of Ci is from 3 to more than 20%, preferably from 10 to less than 100%, more preferably from 30 to less than 30%.

The silver chloride content contained in the chlorobromide phase contained in the emulsion grains of the present invention: more than 100%, preferably 70 to 0000
It is a mole rice cake, more preferably 10 to 10 mole rice cake. As mentioned above, the minimum image density of silver chlorobromide emulsions tends to increase, and this is particularly noticeable as the content of silver chloride increases.

Therefore, if the silver chloride content is less than j%, even if there is microscopic non-uniformity of silver chloride, the width of its distribution is substantially small and does not cause much trouble.

However, when the silver chloride content is 3 moles or more, the minimum a degree tends to increase in conventional grains in which silver chloride is microscopically non-uniformly distributed. Therefore, in this case, it is not possible to take advantage of the rapid processability characteristic of silver chlorobromide. However, with the silver halide grains of the present invention having a "completely uniform" silver chloride distribution, all the advantages of containing silver chloride can be utilized, and the developing speed and fixing speed can be increased, which could not be achieved with method 1. In addition, good silver chlorobromide grains (or silver chloroiodobromide) having a small minimum concentration can be obtained.

-/♂-g- Next, a method for producing grains having a completely uniform silver chloride distribution will be described.

The method for producing silver halide grains of the present invention consists of nucleation and grain growth.

1 Nucleation The silver halide grains that form the nucleus of the silver halide of the present invention are described in Chemie et Ph by P. Glafkides.
isiquePhotographique(1'au
I Monte 1, 1967), G, F, Duf.
Photographic Emulsion by fin
Chemistry (The Focal Pres.
s publication, 1966), V, LZelikmanet
Al AuthorMaking and Coatingr'h
otographicEmulsion(The Fo
Cal I'ress, 1964). That is,
Any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble root salt with the soluble chlorine salt may be any one-sided mixing method, simultaneous mixing method, or a combination thereof. .

It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method).

As one form of the simultaneous mixing method, a method in which the pAg in the liquid phase in which silver halide is produced can be kept constant, ie, the so-called Chondrold Double Geno I method can also be used. According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained.

Two or more types of silver halide emulsions formed separately may be mixed and used.

When preparing the nuclei of silver halide grains, it is preferable that the halogen composition be constant, and preferably a double jet method or a control double jet method is used.

The pAg when preparing the nucleus varies depending on the reaction temperature and the type of silver halide solvent, but is preferably 5 to 5.
It is 10. Further, it is preferable to use a silver halide solvent because the grain formation time can be shortened. For example, commonly known silver halide solvents such as ammonia and thioether can be used.

The shape of the nucleus may be plate-shaped, spherical, twinned, octahedral, cubic, tetradecahedral, or mixed.

Further, the nuclei may be polydisperse or monodisperse, but it is more preferable that the nuclei be monodisperse. Here, "monodisperse" has the same meaning as described above.

Also, to make the particle size uniform, British patent 1.53
No. 5,016, Special Publication No. 48-36890, No. 52-16
364, etc., a method of changing the addition rate of silver nitrate or alkali halide aqueous solution according to the grain growth rate, U.S. Pat. It is preferable to use a method of varying the concentration of an aqueous solution as described in 2006, and grow quickly within a range that does not exceed the critical supersaturation degree. These methods do not cause re-nucleation and each silver halide grain is coated uniformly, so they are preferably used when introducing a coating layer, which will be described later.

The nucleation method described in "Second Speed" is carried out by adding a silver salt aqueous solution and a halogen salt aqueous solution to a reaction vessel containing an aqueous solution containing a dispersion medium while stirring the dispersion medium well. Nucleation can also be carried out by adding fine-sized particles of silver halide to the reaction vessel without adding an aqueous silver salt solution and an aqueous halide solution to the reaction vessel, or by subsequent ripening. The size of the fine silver halide added is preferably 0.1 μm or less, more preferably 0.06 μm or less, and still more preferably 0.03 μm or less. The method for producing fine silver halide grains is detailed in the Growth section. Fine silver halide grains have a low solubility due to their fine grain size.
When added to the reaction vessel, it dissolves and becomes silver ions and halogen ions again, which are deposited on a small portion of the particles introduced into the reaction vessel to form core particles.

In this nucleation method, a silver halide solvent can be used if necessary, and this will be described later. The nucleation temperature is preferably 50°C or higher, more preferably 6
The temperature is 0°C or higher. Fine grain silver halide may be added all at once or continuously. When continuously added, it may be added at a constant flow rate, or the flow rate may be increased over time.

In the process of nucleus formation or physical ripening of silver halide grains, a metal salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof,
Iron salts or iron complex salts may also be present.

2. After the formation of growth nuclei, an aqueous solution of a water-soluble silver salt and an alkali halide is added to the reaction vessel in order to grow the nuclei so as to prevent new nucleation. In the conventional method, an aqueous solution of silver and halide salts is added into a reactor under efficient stirring. At this time, when growing silver halide with a single halogen composition (for example, silver bromide, silver chloride), the silver halide is completely uniform, and even when observed using a transmission electron microscope, no difference is observed. , no microscopic heterogeneity is observed.

If the composition is originally a single halide, nonuniform growth (apart from dislocations) will not occur in principle, and therefore,
In the growth of pure silver bromide and pure silver chloride, the non-uniformity referred to in the present invention is impossible regardless of the preparation conditions. However, in the growth of silver halides (so-called mixed crystals) having a plurality of nolide compositions, non-uniform growth in the halide compositions becomes a serious problem. It has already been mentioned that the non-uniform distribution of silver iodide can be clearly confirmed by transmission electron microscopy.

On the other hand, various studies have been made to obtain uniform growth of silver halide. It is known that the growth rate of halogenated root particles is greatly influenced by the silver ion concentration, halide salt concentration, and equilibrium solubility in the reaction solution.

Therefore, if the concentrations (silver ion concentration, halide ion concentration) in the reaction solution are non-uniform, the growth rate will vary depending on each concentration, and non-uniform growth will occur. As a method to improve this local concentration bias, US Pat.
The techniques disclosed in No. 415,650, British Patent No. 1,323,464, and US Pat. No. 3,692,283 are known.

These methods include a reaction vessel filled with an aqueous colloid solution, a hollow rotating mixer having a slit in the wall of a medium-thick cylinder (the inside is filled with an aqueous colloid solution, and more preferably the mixer is moved up and down by a disk). ) is installed so that its axis of rotation is vertical,
The halogen salt aqueous solution and the silver salt aqueous solution are supplied from the upper and lower open ends of the supply pipe into the mixer rotating at high speed, and are rapidly mixed and reacted (if there are upper and lower separation discs, The halogen salt aqueous solution and silver salt aqueous solution supplied to the two chambers are each diluted by the colloid aqueous solution filled in each chamber, and are rapidly mixed and reacted near the exit slit of the mixer). This is a method of growing silver halide grains by discharging them into an aqueous colloid solution in a reaction vessel.

However, even with this method, the non-uniform distribution of silver chloride could not be resolved at all, and tree ring-like striped patterns indicating non-uniform distribution of silver chloride were clearly observed using a cooling transmission electron microscope.

On the other hand, Japanese Patent Publication No. 55-10545 discloses a technique for preventing uneven growth by improving local concentration deviation. In this method, a halogen salt aqueous solution and a silver salt aqueous solution are separately supplied through a supply pipe from the lower end of a mixer into which a colloid aqueous solution is dropped into a reaction vessel filled with a colloid aqueous solution. The reaction solution was rapidly stirred and mixed by a lower stirring blade (turbine blade) installed in the mixer to grow silver halide, and then immediately grown by an upper stirring blade installed above the stirring blade. This is a technique in which silver halide particles are discharged from the opening of an upper mixer into an aqueous colloid solution in a reaction vessel. However, even with this method, the non-uniform distribution of silver chloride could not be resolved at all, and tree ring-like striped patterns indicating non-uniform distribution of silver chloride were clearly observed.

Thus, it is clear that completely uniform silver chloride distribution cannot be realized using the techniques disclosed so far. As a result of intensive research, the inventor found that in the growth of silver halide grains containing chloride, the silver ions and halide ions (chlorine ions, bromide ions, and iodine ions) that form the grains are completely added to the reaction vessel as an aqueous solution. By supplying silver halide in the form of fine silver halide particles with the desired halide composition and growing the grains, tree ring-like striped patterns completely disappear and a completely uniform silver chloride distribution can be obtained. I found out. This is a surprising technique that cannot be achieved using conventional methods. More specific methods include: ■ Method of adding fine grain emulsions containing silver chloride prepared in advance. Fine silver halide grains (silver chloride bromide, An emulsion containing silver iodobromide, silver iodochloride) is prepared in advance, and grains are grown by supplying only this fine grain emulsion without supplying any water-soluble silver salt aqueous solution or water-soluble halide aqueous solution to the reaction vessel. urge

■ Method of supplying silver halide fine particles from a mixer outside the reaction vessel As an efficient method for supplying fine particles, a powerful and efficient mixer is installed outside the reaction vessel as shown in Figure 1, and water-soluble roots are added to the mixer. An aqueous solution of a salt, an aqueous solution of a water-soluble halide, and an aqueous protective colloid are supplied and mixed rapidly to generate extremely fine silver halide particles, which are immediately supplied to a reaction vessel. At this time, as in (2), the aqueous solution of the water-soluble silver salt and the aqueous solution of the water-soluble halogen salt are not supplied to the reaction vessel at all.

U.S. Pat. No. 2,146,938 describes the growth of a phase grain emulsion by mixing coarse particles that have not adsorbed adsorbed substances with fine particles that have not adsorbed adsorbed substances, or by slowly adding a fine grain emulsion to a coarse grain emulsion. A method is disclosed. However, only silver iodobromide is dealt with here.

U.S. Pat. No. 3,317,322 and U.S. Pat. No. 3,206,313 disclose that a silver halide grain emulsion serving as a core is chemically sensitized to have an average grain size of at least 0.8 μm, and is chemically sensitized to have an average grain size of 0.4 μm or less. A) Forming a shell by mixing silver halide grain emulsions that have not been
A method for preparing silver halide emulsions with high internal sensitivity is disclosed. This patent is concerned with silver bromide and silver iodobromide with a low silver iodide content, and is quite different from this patent which is concerned with grains containing silver chloride. JP-A-58-111936 discloses that [instead of introducing silver and halide salts as an aqueous solution, silver and halide salts are introduced initially or in the growth stage in the form of fine silver halide grains suspended in a dispersion medium. be able to. The particle size is such that it readily undergoes Ostwald ripening onto larger particle nuclei that may be present when introduced into the reactor. Silver bromide, silver chloride and/or mixed silver halide grains can be introduced. ” is stated. However, these are general descriptions of silver halide growth;
There is no teaching of specific manufacturing methods or specific examples necessary for preparing completely uniform silver halide grains as referred to in this patent.

Next, each method will be explained in detail.

■About the method In this method, grains that will serve as a nucleus or core are made to exist in a pre-warming reaction vessel, and then an emulsion containing finely sized grains prepared in advance is added and the fine grains are dissolved by so-called Ostwald ripening. Its deposition in the nucleus or core causes particle growth. The halide composition of the fine grain emulsion contains silver chloride that is the same as the silver chloride content of the target grains, which are silver chlorobromide, silver chloroiodobromide, and silver iodochloride. The particle size is preferably 0.1 μm or less in average diameter, more preferably 0.1 μm or less.
06 μm or less. In the present invention, the dissolution rate of the fine particles is important, and in order to increase the dissolution rate, it is preferable to use a silver halide solvent.

Examples of the silver halide solvent include water-soluble bromides, water-soluble chlorides, thiocyanates, ammonia, thioethers, and thioureas.

For example, thiocyanate (US Pat. No. 2.222264, US Pat. No. 2.448.53/1, US Pat. No. 3.320.06)
9, etc.), ammonia, thioether compounds (e.g., U.S. Pat. No. 3,271.157, U.S. Pat. No. 3,574..6)
No. 28, No. 3,704.130, No. 4,297.
439, 4.276.347, etc.), 1,000-ion compounds (for example, JP-A-53-144319, JP-A-53-8)
2408, 55-77737, etc.), amine compounds (e.g., JP-A-54-100717, etc.), 1,000-urea derivatives (e.g., JP-A-55-2982), imidazoles (e.g., JP-A-54-100717) , substituted mercaptotetrazole (for example, JP-A-57-202531).

The temperature at which silver halide grains are grown is 50°C or higher, preferably 60°C or higher, more preferably 70°C or higher.
It is above °C. In addition, fine grain emulsion in crystal growth is
-Although it may be added at one time or in parts, it is preferable to feed at a constant flow rate, and more preferably to increase the rate of addition. In this case, how to increase the addition rate depends on the concentration of coexisting colloids, the solubility of silver halide crystals, the size of halide 1iFA fine particles, the degree of agitation of the reaction vessel, the size and concentration of crystals present at each point, Hydrogen ion concentration (p
H), &Fi ion concentration (pAg), etc., and is determined from the relationship between the target crystal particle size and its distribution, and can be easily determined by a routine experimental method.

Regarding (2), the crystal growth method disclosed in the present invention, as previously described, involves adding silver ions and halide ions (including chloride ions) necessary for silver halide crystal growth to an aqueous solution thereof in the conventional manner. Rather than supplying silver halide grains as a grain, fine silver halide crystals are added and their high solubility is utilized to induce Oswald ripening, thereby growing silver halide grains. In this case, the rate-determining step in the system is not the growth rate of silver halide grains, but how quickly the fine grains dissolve and supply silver ions and halide ions into the reaction vessel. ■
When preparing an emulsion with roughly fine grains, as in
On the other hand, as silver halide grains become smaller in size, their solubility increases and they become extremely unstable, causing formation of grains by themselves, resulting in an increase in grain size.

James (T, tl, James), The Theory
Of the Photographic Process, 4th edition contains Lippmann emulsions as fine grains.
ulsion) is cited, and its average size is 0.05μ
It is stated that m. Although it is possible to obtain fine particles with a particle size of 0.05 μm or less, even if obtained, the particles are unstable and the particle size easily increases due to Ostwald ripening. Although the above-mentioned Ostwald ripening can be prevented to some extent by adsorbing the adsorbate, the rate of bone dissolution also decreases, which is contrary to the intention of the present invention.

In the present invention, this problem was solved by the following three techniques.

After forming fine particles in a mixer using the apparatus shown in Figure 1,
Immediately add it to the reaction vessel.

After forming fine grains in advance to obtain a fine grain emulsion, it is redissolved, and the dissolved fine grain emulsion is added to a reaction vessel that holds silver halide grains serving as the core and in which a silver halide solvent is present to prevent grain growth. What happened was mentioned in ■. However, once the extremely fine particles are generated, they undergo Ostwald ripening during the particle formation process, water washing process, redispersion process, and redissolution process, resulting in an increase in the particle size. In this method, this Ostwald ripening occurs by providing a mixer very close to the reaction vessel and shortening the residence time of the additive liquid in the mixer, thereby immediately adding the generated fine particles to the reaction vessel. I tried not to. Specifically, the residence time t of the liquid added to the mixer is expressed as follows.

Addition amount (mff/m1n) In the production method of the present invention, it is at most 10 minutes, preferably at most 5 minutes, more preferably at most 1 minute, even more preferably at most 20 seconds. The fine particles thus obtained in the mixer are immediately added to the reaction vessel without their particle size increasing.

Perform powerful and efficient stirring using an O mixer.

James (T, Il, James) The Theory of Observation I Graphic Process p, p. 93 states, ``Along with male 1 to walt aging, another form is coalescence.In coalescence aging, There is a sudden change in grain size as crystals that were previously far apart come into direct contact and coalesce to form larger crystals.Both Ostwald ripening and Coalescence ripening occur not only after the end of deposition, but also during deposition. The coalescence ripening described here is particularly likely to occur when the particle size is very small, and especially when stirring is insufficient. In extreme cases, it may even create coarse, clumpy particles. In the present invention, the second
As shown in the figure J, since a closed type mixer is used, the stirring blade in the reaction chamber can be rotated at a high rotational speed, which was not possible with a conventional open type reaction vessel. (If the stirring blades are rotated at high speeds, the liquid will be blown away by the centrifugal force, which will also cause the problem of foaming, making it impractical.) Powerful and efficient stirring and mixing can be performed, and the above-mentioned core sistance μm formation can be achieved. As a result, fine particles with extremely small particle sizes can be obtained. In the present invention, the rotation speed of the stirring blade is 1000r, p, m or more, preferably 2000r, p,m or more, more preferably 3000r
, p, m or more.

Injection of protective colloid aqueous solution into mixer The aforementioned coalescence ripening can be significantly prevented by protective colloid of silver halide fine particles. In the present invention, the protective colloid aqueous solution is added to the mixer by the following method.

■ Inject the protective colloid aqueous solution alone into the mixer.

The concentration of the protective colloid is preferably 1% by weight or more, preferably 2% by weight or more, and the flow rate is at least 20%, preferably at least 50% of the sum of the flow rates of the silver nitrate solution and the aqueous halide solution.
More preferably, it is 100% or more.

■ Zet a protective colloid in a halogen salt aqueous solution.

The concentration of the protective colloid is at least 1% by weight, preferably at least 2% by weight.

■ Add a protective colloid to the silver nitrate aqueous solution.

The concentration of the protective colloid is at least 1% by weight, preferably at least 2% by weight. When gelatin is used as a protective colloid, it is better to mix the silver nitrate solution and the protective colloid solution immediately before use, since gelatin silver is made from antiion and gelatin, and silver colloid is produced by photolysis and thermal decomposition.

Further, the above methods (1) to (4) may be used alone or in combination, or three may be used at the same time. As the protective colloid used in the present invention, gelatin is usually used, but other hydrophilic colloids can also be used.
It is described in section ■.

Thus, the particle size of the fine particles obtained by the techniques ① to 0 can be confirmed by placing the particles on a mesh and using a transmission electron microscope at a magnification of 20,000 to 40,000 times. The size of the fine particles of the present invention is 0.06 μm or less, preferably 0.06 μm or less.
0.03μm or less, more preferably 0.011! m or less.

In this way, it becomes possible to supply particles of extremely fine size to the reaction vessel, resulting in a higher dissolution rate of fine particles,
Therefore, higher growth rates of silver halide grains in the reaction vessel can be obtained. Although the method no longer requires the use of silver halide solvents, silver halide solvents may be used if desired to obtain higher growth rates or for other purposes. The silver halide solvent is as described in Method (2). According to this method, the supply rate of silver ions and halide ions to the reaction vessel can be freely controlled. Although a constant feed rate may be used, it is preferable to increase the addition rate. The method is
No. 890 and No. 52-16364. The rest is as stated in ■Law. Furthermore, according to this method, the halogen composition during grain growth can be freely controlled; for example, during grain growth, the silver chloride content can be maintained at a constant level, the silver chloride content can be continuously increased or decreased, or the silver chloride content can be continuously increased or decreased. It becomes possible to change the silver chloride content at this point.

The reaction temperature in the mixer is preferably 60°C or lower, preferably 50°C or lower, more preferably 40°C or lower. At a reaction temperature of 35° C. or lower, ordinary gelatin tends to coagulate, so it is preferable to use low molecular weight gelatin (average molecular weight of 30,000 or lower).

The low molecular weight gelatin used in the present invention can usually be produced as follows. Gelatin, which is commonly used and has an average molecular weight of 100,000, is dissolved in water, and a gelatin-degrading enzyme is added to enzymatically decompose the gelatin molecules. For information on this method, see R.J. Cox, PhotographicGe.
lationlT Academic Press
, London, 1976\P, 23
3-251, P, 335-346 can be referred to. In this case, since the bonding position is determined to be decomposed by the enzyme, a low molecular weight gelatin with a relatively narrow molecular weight distribution can be obtained, which is preferable.

In this case, the longer the enzymatic decomposition time, the lower the molecular weight. In addition, there is also a method of heating and hydrolyzing in a low pH (p + l 1 to 3) or high pH (p + -110 to 12) atmosphere.

Next, the structure of the silver halide grains of the present invention will be explained.

The internal latent image type silver halide emulsion which is not pre-sifted and is used in the present invention is an emulsion containing silver halide in which the surface of the silver halide grains is not pre-sifted and the latent image is mainly formed inside the grains. However, more specifically, the silver halide emulsion is added to the transparent support by 0.5 to 3
g/nζ, exposed to light for a fixed time of 0.01 to 10 seconds, and developed for 5 minutes at 18°C in the following developer A (internal developer). The maximum density measured by the method is obtained when a silver halide emulsion coated in the same amount and exposed in the same manner as in Section 2 is developed in the following developer B (surface type developer) at 20°C for 6 minutes. preferably at least 5 times greater, more preferably at least 1
It has a concentration 0 times greater.

Surface developer B Metol 2.5g! -Ascorbic acid 10gN aB Oz ・41
-120 35gKBr
Add 1g water
1p internal developer A Metol 2g Sodium sulfite (
anhydrous) 90g Hyde t-I quinone
8g Soda carbonate (-water salt)
52.5gKBr
5gKI
O, add 5g water
Specific examples of LA internal type emulsions include British Patent No. 1,011,062 and US Patent No. 2.592゜250.
Examples include conversion type halogen l emulsions and core/shell type silver halide emulsions, which are described in specifications such as No. As for JP-A-47-32813
No. 47-32814, January 52-13472,
No. 5360222, No. 53-66218, No. 536
No. 6727, No. 57- ], No. 3664.1, No. 58
-70221, 59-208540, 5! If
-216136, same GO-107641, same 60
-247237, 61-21.18, 61-3
No. 137, Special Publication No. 56-18939, 58-14.1
No. 2, No. 58-1415, No. 58-6935, No. 5
No. 8-108528, Japanese Patent Application No. 61-36424, U.S. Pat. No. 3,206.313, U.S. Pat. No. 3.317,322
No. 3,761.266, No. 3,761.27
ri No. 3.850.637, No. 3,923.
No. 513, same No. 4. ．． No. 035,185, No. 4.39
No. 5478, No. 4,431,730, No. 4゜50
4. No. 570 European Patent No. 0017148, Research Disclosure Magazine RD], 6/12 3rd issue J (/77/77), same A/Ryo/Ma 3rd issue (/
(March 7), deleted f6. ．． Examples include emulsions described in 23j No. 10 (/g3/July).

In the present invention, it is particularly preferable to use a core-shell type emulsion. The core and shell compositions may be the same or different.

The total silver chloride content of the emulsion grains of the present invention is 3 mol or more, but more effective is 70 mol or more and 0 mol or less. More preferably, go at least 20 moles of steamed rice.
Less than a molar amount.

The silver halide used in the present invention preferably does not contain silver iodide, or even if it does contain it, it is preferably 10 moles or less.

The average grain size of the silver halide grains (determined by the diameter of a sphere with the same volume as the grain) is preferably less than /Sμ and more than Ol-μ, and particularly preferably less than /1.2μo, more than pμ. be. The particle size distribution may be narrow or wide, but in order to improve granularity and sharpness, the particle number or Keiyo should be within ±40% of the average particle size, more preferably ±30%. 90% or more, especially 95% or more of all particles fall within a narrow particle size distribution (most preferably within ±20%);
So-called "monodisperse" silver halide emulsions are preferably used in the present invention. In addition, in order to satisfy the target gradation of a light-sensitive material, two or more types of monodisperse silver halide emulsions with different grain sizes or multiple types of monodisperse silver halide emulsions with the same size but different sensitivities are used in an emulsion layer having substantially the same color sensitivity. The particles can be mixed in the same layer or coated in separate layers.

Furthermore, two or more types of polydisperse silver halide emulsions or a combination of a monodisperse emulsion and a polydisperse emulsion may be mixed or layered for use.

The shape of the silver halide grains of the present invention may be regular crystal shapes such as octahedral or tetradecahedral, or irregular crystal shapes such as spherical.
ar) may have a crystalline form.

Further, tabular grains may be used, and in particular, an emulsion may be used in which tabular grains having a length/thickness ratio of 5 or more, particularly 8 or more account for 50% or more of the total projected area. Further, an emulsion having a composite form of these crystal forms or a mixture thereof may be used.

The silver halide emulsion used in the present invention can be chemically sensitized inside or on the grains by sulfur or selenium sensitization, reduction sensitization, noble metal sensitization, etc. alone or by (i) 1).

In particular, in the case of core-shell particles, one or more of the above chemical sensitization methods may be used for the core. Alternatively, metals such as 1r, Pd, Rh, etc. may be used. It is not necessary to chemically sensitize the shell, but it is a shame to do so.

For detailed specific examples, see Research Disclosure Magazine No. 17643-n (published December 1978) P.
It is in the patent described in 23 etc.

The photographic emulsions used in the present invention are spectrally sensitized with photographic sensitizing dyes by conventional methods. Particularly useful pigments are pigments belonging to cyanine pigments, merocyanine pigments, and composite merocyanine pigments, and these pigments can be used alone or in combinations of three,
Can be used together. Further, the dyes listed in 1U may be used in combination with a supersensitizer. For detailed specific examples, see Research Disclosure magazine No. 17643-TV (1978
(Published in December 2016) in the patent described on pages 23-24.

By making the distribution of silver chloride completely uniform in this technique, lower minimum concentrations can be obtained for conventional non-uniform grains. In this technology, the reason why the microscopic uniformity of the silver chloride is important is that the electrons generated by light move more easily and more efficiently than when the electrons are non-uniform, so they can embed themselves inside the grain (core part). This is thought to be due to the concentration of images.

The photographic emulsion used in the present invention contains henzene thiosulfonic acids, henzene sulfinic acids, and A carbonyl compound etc. can be contained.

For more detailed examples of antifoggants or stabilizers and their uses, see, for example, U.S. Pat. No. 3,954.
474th place, same No. 3. 982. No. 9, 17, Tokuko Showa 5
No. 2-28660, Research Disclosure (R
D) Magazine 17643 (]99781 December VIA ~V
JM and H., J. Birr [StabilizaLion of Silver Halide Photographic Emulsions 1]
of Photographic 5ilver 1l
Focal Press, published in 1974, etc.

A variety of color couplers can be used to form direct positive color images in the present invention. A color coupler is a compound that generates or releases a substantially non-diffusible dye through a coupling reaction with an oxidized form of an aromatic primary amine color developer, and is itself a substantially non-diffusible dye. Preferably, it is a compound. Typical examples of useful color couplers include nano-1-ol or phenolic compounds, pyrazolone or biraduroazole compounds, and open-chain or heterocyclic ketomethylene compounds. Specific examples of these cyan, magenta, and yellow couplers that can be used in the present invention are given in "Resachi Disc I Codger" magazine, 17643r, published in December 1978), p.25.
It is described in the compounds and patents cited therein in Section 1-2, No. 1871.7 (issued in November 1979) and JP-A-62-215272.

Colored couplers to correct unnecessary absorption in the short wavelength range of the dyes produced, couplers in which the coloring dye has appropriate diffusivity, non-coloring couplers, DIR couplers that release a development inhibitor upon coupling reaction, and Polymerized couplers can also be used.

As the binder or protective colloid that can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention, it is advantageous to use seratin, but other hydrophilic colloids can also be used.

A color antifogging agent or a color mixing inhibitor can be used in the light-sensitive material of the present invention.

Representative examples of these are JP-A No. 62-215272 600~
It is described on page 63.

Various anti-fading agents can be used in the photosensitive +J material of the present invention.

A representative example of these anti-fading agents is disclosed in Japanese Patent Application Laid-Open No. 62-21527.
No. 2, pages 400-440.

The photosensitive material of the present invention includes a dye that prevents irradiation and halation, an ultraviolet absorber, a reversible agent, a fluorescent whitening agent, a capping agent, an air fog prevention agent, a coating aid, a hardening agent, and an antistatic agent. It is possible to add additives, shearability improvers, etc. Typical examples of these additives are Research Disclosure Magazine Sections 7643 - xm (published December 1978)
p25-27, and 18716 (November 1979)
Published in May), pages 647-651.

The light-sensitive material according to the present invention includes, in addition to the silver halide emulsion layer,
Protective layer, intermediate layer, filter layer, antihalation agent,
It is preferable to provide an auxiliary layer such as a thick layer or a white reflective layer as appropriate.

In the photographic light-sensitive material of the present invention, the photographic emulsion layer and other layers are published in Research Disclosure Magazine No. 17643XV.
Item 11 (issued December 1978) 228, European Patent No. 0.182,253, and JP-A-61-
97655. Also, Research Disclosure Magazine Section 176.13XV P28
The coating methods described in items 1 to 29 can be used.

The present invention can be applied to various color photosensitive materials.

For example, representative examples include color reversal film for slides or television, color reversal paper, and instant color film. It can also be applied to full-color copying machines and color hard copies for storing images on CRTs. The present invention also applies to "Research Disclosure" magazine No. 1712.
The present invention can also be applied to black-and-white light-sensitive materials using a mixture of three color couplers as described in No. 3 (published July 1978).

Furthermore, the present invention can also be applied to black and white photographic +J materials.

Black and white (B/W) photographic materials to which the present invention can be applied include JP-A-59-208540 and JP-A-60-2600.
B/W direct positive photographic material described in 39 (
For example, there are X-ray photosensitive materials, dupe photosensitive materials (A, micro photosensitive materials, phototypesetting photosensitive materials, printing texture) and the like.

The direct positive photographic light-sensitive material of the present invention is subjected to a fogging process as shown below after imagewise exposure.

As mentioned above, the fogging process is a method of exposing the entire surface of the photosensitive layer called the "light fogging method" and a method of developing in the presence of a nucleating agent called the "chemical fogging method". Either of these may be used. Development may be carried out in the presence of a nucleating agent and fogging light. Alternatively, a light-sensitive material containing a nucleating agent may be exposed to light.

In the present invention, it is particularly preferable to perform a nucleating treatment with a nucleating agent.

The entire surface exposure, that is, the fogging exposure in the "light fogging method" of the present invention is carried out after the imagewise exposure and/or during the development process. The imagewise exposed light-sensitive material is immersed in a developer solution or a pre-bath of the developer solution, or is taken out from the solution and exposed before drying, but it is most preferable to expose the material in the developer solution.

As a light source for fogging exposure, a light source with a wavelength circle to which the photosensitive material is sensitive may be used, and generally any of fluorescent lamps, tungsten lamps, xenon lamps, sunlight, etc. can be used.

These specific methods are described in, for example, the British patent], 151.
No. 363, Special Publication No. 45-12710, No. 45-127
No. 09, No. 58-6936, JP-A No. 48-9727, No. 56-137350, No. 57-129438,
It is described in US Pat. No. 58-62652, US Pat. No. 5B-60739, US Pat. No. 4,440,851, US Pat.

As the nucleating agent used in the present invention, all compounds developed for the purpose of nucleating endothermic silver halide can be used. Two or more types of nucleating agents may be used in combination. To explain in more detail, examples of nucleating agents include, for example, [Research Disclosure J].
Closure) Magazine, No. 22534 (1983
(Published in January 2016) pp. 50-54, same magazine, floor 15162 (1
Published in November 1976) pages 76-77, and the same magazine, No.
23510 (published in November 1983), pages 346 to 352, these include quaternary heterocyclic compounds (hereinafter referred to as (N-1,1)) and hydrazine compounds (hereinafter referred to as (N-11)). ) and other compounds.

Specific examples of the above [N-■] are given below.

(Nl-1) 5-ethoxy-2-methyl-1-propargylquinolinium BromiF (N-1-2) 2.4-dimethyl-1-propargyldi)-solinium Bromide (N-■-3) 2-Methyl -1, -13-C2(
4-Methylphenyl)hydrazonocobutyl)quinolinium iosito (N-I-4) 3,4-dimethyl-dihydropyrosito (2,lb) hendithiazolium bromide (N-1-5) 6-nitoxydi Ocarponylamino-2-methyl-1-propargylquinolinium trifluoromethanesulfonate (N (N (N (N 1-6) 2-methyl-6-(2-phenylthioureido)-1-propargylquinolinium) Norinium Promide 1-7) 6-(5-penditriazole-lupoxamide)-2-methyl 1-propargylquinolinium I.Lifluoromethanesulpona-1.1-8) 6-C3-(2-Mercapto ethyl)
ureido]-2-methyl 1-propargylquinolinium trifluoromethanesulfonate 1-9) 6-[3-[3-(5-mercapto-1
．． 3.4-thiadiazol-2-ylthio)propargyl-2-methyl-1-propargylquinolinium trifluoromethanesulpo-note 1-10) 6-(5-mercaptotetrazole-
Specific examples of 1-yl)-2-methyl 1-propargylquinolinium (N (N (N iodine F)) are shown below.

IT-1. )]-]formyl-2-(/l-C
3(2-Me(·xyphenyl)ureidodiphenyl)hydrazine H-2) 1-pormyl-2- (4- [3(:
l C3-(2.4-di-tert-hentylphenoxy)propyl]ureido)phenylsulfonylaminocophenyl)hylazine(N-11 (N-11 (N ■ 3) 1-pormyl-2-( 4, [3(5-mercaptotetrazol-1-yl)hensamido]phenyl)hydrazine4) 1-formyl-2- (4- (3C3-(5
-mercaptotetrazol-1-yl)phenyl]ureido)phenyl]hydrazine5) 1-formyl-2- (1- (3(N --4 methyl-C2,4-1-riazyl-3-yl)carbamoyl)propanamide) phenyl]hydrazine ■-formyl-1-(4,-[3 IN-(4-(3-mercapto 1, 2.4) -triazol-4yl)phenylcarbamoyl)propanamideraphenyl)hydrazine1-formyl-2-C4,-(3CN-(5-mercapto-134-deadiazol-2-yl)carbamoyl]propanamido)phenyl]- Hydrazine 2-[4-henzutriazole5-carboxamido)phenyl] 1-pormylhydrazine9) 2-(4-+3-(N-(henzu1~riazuru5-carboxyrimito')carbamoyl]propanamide)phenyl]- 1-pormylhydrazine (N-TI-10) 4-formyl-2-(4-[1
[N-phenylcarbamoyl) thiosemicarbamide] phenyl] Hydrazine and other hydrazine-based nucleating agents include, for example, JP-A No. 5
No. 7-86829, U.S. Patent No. 4.560.638;
No. 4,418,928, and No. 2,563,7
No. 85 and No. 2.588982.

In the present invention, in order to further promote the action of the nucleating agent, the following nucleating promoters can be used.

As the nucleation accelerator, compounds having at least one mercapto group optionally substituted with an alkali metal atom or an ammonium group, such as TeI-ragindenes, triazaindenes, and pentazaindenes, and JP-A-62 -10
The compounds described in No. 6656 can be added.

The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component.

As this color developing agent, aminophenol compounds are also useful, but p-phenylenediamine compounds are preferably used, and a representative example thereof is 3-methyl-4-
Amino-N-N, diethylaniline, 3-methyl-4-
Amino-N-ethyl N-β-hydroxyethylaniline, 3-methyl4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N-β- Methoxyethylaniline and its sulfate, hydrochloride or p-toluenesulfonate are mentioned. Two or more of these compounds can be used in combination depending on the purpose.

The pH of these color developing solutions is 9 to 12, preferably 9.5 to 11.5.

After color development, the photographic emulsion layer is usually bleached.

The bleaching process may be carried out simultaneously with the fixing process (bleach-fixing process) or separately. Furthermore, in order to speed up the processing, a processing method may be used in which bleaching is followed by bleach-fixing. Furthermore, treatment in two continuous bleach-fixing baths, fixing treatment before bleach-fixing treatment, or bleaching treatment after bleach-fixing treatment can be carried out as desired depending on the purpose.

The silver halide color photographic photosensitive plate 81 of the present invention is generally subjected to a water washing and/or stabilization process after being desilvered. The amount of water used in the washing process depends on the characteristics of the photosensitive material (for example, depending on the amount of couplers, etc. used), the application, and the temperature of the washing water.
It can be set over a wide range depending on the number of water washing tanks (number of stages), replenishment methods such as countercurrent or forward flow, and various other conditions. Among these, the relationship between the number of washing tanks and the amount of water in the multistage countercurrent method is as follows:
Journal of the 5ociety of
Motion Picture and Te
levisionlEngineers Volume 64, r'
, 248-253 (May 1955 issue).

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up processing. In order to incorporate the color developing agent, it is preferable to use various precursors of the color developing agent.

On the other hand, various known developing agents can be used to develop the black-and-white light-sensitive material of the present invention. That is, polyhydroxyhensens, such as hydroquinone, 2
-chlorohydroquinone, 2-methylhydroquinone,
Catechol, pyrogallol, etc.; aminophenols,
For example, p-aminophenol, N-methyl-p-aminephenol, 2,4-diaminophenol, etc.; 3-pyrazolidones, such as 1-phenyl-3-pyrazolidones, ■-phenyl-4,4'-dimethyl-3-pyrazolidone, 1 -phenyl-4-methyl 4-hydroxymethyl-3
-pyrazolidone, 5゜5-dimethyl-1-phenyl-3
- Pyrazolidone, etc.; ascorbic acids, etc., can be used alone or in combination. Also, JP-A-58-559
The developer described in No. 28 can also be used.

For detailed examples of developers, preservatives, buffers, and development methods for black and white photosensitive materials, and how to use them, see
Research Disc 1 Cozier” Magazine No. 1764
．． 3 (published in December 1978) as described in sections XIX to XM.

(Example) The present invention will be further explained below with reference to Examples.

Example 1 Preparation of Emulsion 1 Add 3,4-dimethyl-4 to a 3,0% by weight gelatin solution 1.2a containing 0.065M potassium bromide and 0.3M sodium chloride while stirring it. -Thiazoline-2,000 ions of methanol solution at 80 mf! Add 75℃
Add 50cc of 03M silver nitrate solution and 0.03M silver nitrate solution to a reaction vessel maintained at
5 Qcc of an aqueous halogen salt solution containing 18M potassium bromide and 0.8M sodium chloride was added over 3 minutes using a double jet method.

This results in 0.3. Nucleation was performed by obtaining silver chlorobromide grains with a silver chloride content of +1m and a silver chloride content of 40 mol%.

Subsequently, 20 cc of an aqueous solution containing 3.5 g of silver nitrate, 1.5 g of potassium bromide, and 1.
2Qcc of an aqueous solution containing 0g of sodium chloride was simultaneously added by double jet. The particles were monodisperse particles of 0.4μ. A core chemical sensitization treatment was carried out by adding 6 μl of thiosulfuric acid per mole of silver and 7111 g of chloroauric acid (tetrahydrate) to this emulsion and heating at 75° C. for 80 minutes.

The thus obtained core was further heated at 75°C with 140 cc of an aqueous solution containing 26°4 g of silver nitrate, 140 cc of an aqueous solution containing 11.0 g of potassium bromide, and 7.6 g of thorium chloride.
cc was added at the same time by a double jet method to finally obtain silver chlorobromide octahedral particles having an average particle size of 0.7 μm and a silver chloride content of 40 mol %.

This emulsion contains 1.5+ ng of thiosulfate per mole.
The shell was chemically sensitized by adding aluminum and 1.5 μm of chloroauric acid (tetrahydrate) and heating at 60° C. for 60 minutes to obtain internal latent image type halogenated emulsion 1.

Emulsion 2 Preparation Silver chlorobromide fine grain emulsion 2-A O,0] was added to 1.3 p of a 2.3 wt% gelatin solution containing M potassium bromide and 0.05 M thorium chloride while stirring. 600 mff of each of a 1.2 M silver nitrate aqueous solution, a halogen salt aqueous solution containing 0.72 M potassium bromide, and 1.0 M thorium chloride was prepared using the double-shot method.
was added over 25 minutes. During this time, the gelatin solution in the reaction vessel was maintained at 35°C. After this, the emulsion was washed using the usual flow method: 1.:1 to 1.
was added and after dissolution, the pH was adjusted to 6.5. The obtained silver chlorobromide fine particles (silver chloride content 40%) had an average particle size of 0.09 μm.

After carrying out nucleation in the same manner as in Emulsion 1 to obtain silver chlorobromide core particles of 0.3 μm, fine grain emulsion 2-A (silver chloride content: 40 mol%) dissolved at 75°C was pumped into a reaction vessel. added to. The fine grain emulsion was added over 3 minutes at an addition rate of 3.5 g in terms of silver nitrate. At this time, 20 g of thorium chloride was dissolved in advance in the fine grain emulsion. The particles were monodisperse particles with a particle size of 0.4 μm. This emulsion contains 61 μm of thiosulfate per mole.
Add aluminum and 7■ chlorauric acid (dihydrate salt) and heat at 730C.
Chicoa chemical sensitization treatment was performed by heating for 0 minutes.

Further, dissolved fine grain emulsion Co-A was added to the thus obtained core into the reaction vessel using a pump. The addition rate is converted to the amount of silver nitrate! The fine grain emulsion was added over 23 minutes so as to obtain B and G2.

In this way, silver chlorobromide octahedral grains having an average particle size of 0.7 μm and a silver chloride content of μθ mol % were finally obtained.

To this emulsion were added 1 mole of silver υ/, S ~ sodium thiosulfate and i, t ~ chloroauric acid (hydrochloride) at 20°C.
The shell was chemically sensitized by heating for a minute to obtain an internal latent image type silver halide emulsion.

Preparation of Emulsion 3 After carrying out nucleation in the same manner as in Emulsion 3 to obtain silver chlorobromide core grains of 0.3 μm, the seed crystals were grown using the apparatus shown in FIG. A powerful and efficient mixer installed near the reaction vessel produces 3.3? An aqueous solution containing silver nitrate of 20r:c and/or 3? Aqueous solution containing 7.07% potassium bromide and 7.07% sodium chloride, 20CC and 70% by weight low molecular weight gelate/(average molecular M20,000) water bath liquid, 2oCc
was added by triple diet IIA. Ultrafine particles (average size o, o, 2
μm) was continuously introduced into the reaction vessel immediately from the mixer. During this time, the temperature of the mixer was maintained at 2j0C, and the temperature of the reaction vessel was maintained at 73C.

This particle is 0. Monodisperse particles were <1 μm.

This emulsion is worth 1 mole of silver! Core chemical sensitization treatment was performed by adding 16 mv of sodium thiosulfate and 77 ng of chloroauric acid (Horosulfate) and heating at 7 s'c for ♂O minutes.

A shell was further formed on the thus obtained core in the following manner. 26.41.1 of a water bath solution containing silver nitrate/4 LOcc/// for 23 minutes in a strong and efficient mixer placed next to a reaction vessel similar to that described above.

01 potassium bromide and 7. A water bath solution containing sodium chloride of ASi'/HiroOCC and a 70% by weight low molecular weight gelatin (average molecular weight) aqueous solution/1 lOcc were added by a triple jet method. Ultrafine particles (average size 0.0-μm) produced by stirring and reaction in the mixer were immediately and continuously introduced into the reaction vessel from the mixer. During this time, the mixer temperature was 23°C and the reaction vessel temperature was 730°C.

In this way, silver chlorobromide octahedral grains having an average grain size of 0.7 .mu.n1 and a silver chloride content of 0.5 molar were finally obtained.

To this emulsion were added 1)/jmg of sodium thiosulfate and/jmg of chloroauric acid (guhydrate) per mole of silver.
The shell was chemically sensitized by heating at C for 60 minutes to obtain internal latent image type silver halide emulsion 3.

Create the following photographic material using the emulsion.

The support was a paper support (700 μm thick) laminated on both sides with polyethylene, and the coated side contained titanium white as a white pigment.

(Photosensitive layer composition) What are the ingredients below? / Ink I'I in units of tn
Indicates m. Regarding silver halide, the coating amount is shown in terms of silver.

1st layer (high sensitivity red sensitive layer) Emulsion spectrally sensitized with red sensitizing dye (ExS-/,!,3)/O0/ggelatin 7.00 cyan coupler (
ExC-/) 0. /! Cyan coupler (ExC
-, 2) 0. /j Anti-fading agent (Cpd-r, 3
, μ, 73 equivalents) 0.73 Coupler dispersion medium (Cpd-r) o, o3 2nd layer (protective layer) Acrylic modified copolymer of polyvinyl alcohol (degree of modification 77%) O, O, 2 polymethyl methacrylate Equivalent amount of particles (average particle size - 0 μm), silicon oxide (average particle size J μm)
o,ot gelatin/,! 0
Gelatin hardener (H-/) θ, /7 The seventh layer contains ExZK-/ as a nucleating agent at 10-3% by weight based on the amount of silver halide coated, and Cpd-, 2g as a nucleation accelerator. A large amount of 10-2 weight was used. Additionally, each layer contained Alkanol
0 (manufactured by Inu Nippon Ink Co., Ltd.) was used. This sample using (Cp CI-/ri, -o,, 2/) as a stabilizer in the first layer was designated as sample number 10/.

Sample 10.2.103 was prepared in the same manner as Document 70/, except that emulsion 2.3 was used instead of emulsion /.
And so.

The above sample was passed through a red filter and wedge exposed (i7
io seconds, 200 M5), and then the following treatment was performed.

Color development 133 seconds bleach fixing 4tQ I/Water wash (1) G0〃Water wash (2) ≠0〃 Dry 30〃 3r0C//e 33 1/ 3 // 33 // 3 u 33 // 3 //fO/ J 30077m2 3+20 The washing water replenishment method is to replenish the washing water to the washing bath (2).
A so-called countercurrent replenishment system was adopted in which the overflow liquid of 2) was led to the washing bath (1). At this time, the amount of bleach-fix solution brought into the washing bath (1) from the bleach-fix bath for photosensitive materials is 3
At 3 ml/m2, the ratio of the amount of washing water supplementing light to the amount of bleach-fixing solution brought in was 7 times.

The composition of each treatment liquid was as follows.

Color developer D - Sorbitnaphthalene/sulfo/acid sodium/formalin condensate Etele/diaminetetrakismethylenephononic acid diethylene glycol benzyl alcohol Potassium bromide 0,/j? 0. ．． 209 0, /J? 0.207 /, 3i /,! ? /, 2.0rrtl //;. Od/3. j door l
/ and 0rne O,709 Sodium benzotriazole sulfite N,N-bis(carboxymethyl)hydrazine D-glucosetriethanolamine N-ethyl-N-(β-methanenulfonamidoethyl)-3-methyl monoguaminoaniline sulfate Potassium salt carbonate fluorescent whitening agent (diaminostilbene type) 0.003f 2.4t? ≠, 02 2.0? T, or Otsu, 4t? 30, Of 7.07 o, oo4ty 3.2? ! , 3y co, g2 ni, 07 g, 5y 2j, OV /, , 2f cosodium disodium hydrate ethylenediamine≠acetic acid.

Fe(III)・Ammonium・-hydrate Ammonium thiosulfate (700t/II) Sodium p-toluenurphinate Sodium bisulfite! -Mercapto/3゜gutriazole ammonium nitrate 70.0? / l0m1 4#, 0? 33.0? 0.31 10.0? Bleach-fix solution ethylene diamine ≠ acetic acid / -7θ lb to mother liquor Washing water Mother liquor and replenisher both tap water and H-type strongly acidic cation exchange resin (Amberlite IR-/aoB manufactured by Rohm and Haas) 7/-7. OH type anion exchange resin (Amberlite IR-
1100) to reduce the concentration of calcium and magnesium ions to below 3/l, followed by 20 mg of sodium incyanurate dichloride.
/β and (iWj H sodium/, 3Y/(l) were calculated. The pI (i was in the range of &,j~7°3).

The degree of cyan color development of the obtained direct positive image was measured, and the results are shown in Section 7.

Sample 10.2.103 of the present invention has a maximum image density (Dm
ax) is high and the minimum surface (!rJa-e (Dmin
) Preferable results can be obtained by reducing 75.

Example 2 The following photographic material was prepared using Emulsion 1.

The support is a paper support (thickness 100 μm) laminated on both sides with polyethylene 1, and the coated side contains Chikun Why I. as a white pigment.

(Photosensitive layer composition) The components and coating amounts in g/m' are shown below.

Regarding silver halide, the coating amount is shown in terms of silver.

1st layer (high sensitivity red sensitive layer) Emulsion 1 spectrally sensitized with red sensitizing dyes (ExS-1, 2, 3) 0.14 gelatin 1.00 cyan coupler (E
x C-1,) 0. ], 5 cyan coupler (ExC-2) 0.1.5 anti-fading agent (Cp
d-2, 3, 4, 13 equivalents) 0.15 Coupler dispersion medium (Cpd-5) 0.03 Coupler solvent (Solv-7, 2, 3 equivalents) 0, 10 2nd layer (protective layer) Vol. Acrylic modified copolymer of hinyl alcohol (degree of modification 17%) 0.02 Polymethyl methacrylate particles (average particle size 2.4 microns), silicon oxide (average particle size 5 microns) etc.i 0.
05 Gelatin 1.50 Gelatin hardener (H-1) 0.17 Each layer contains alkanol -1
20 (manufactured by Inuhiki Ink Co., Ltd.) was used. (Cpd-19, 20, 21) was used as a stabilizer in the first layer. This sample was designated as sample number 201.

Samples 202 and 203 were obtained by using emulsion 2.3 instead of emulsion 1 in sample 201.

These samples were passed through a red filter and subjected to wedge exposure (1
/10 seconds 20CMS), and then the same treatment as in Example 1 was performed. At that time, 0.5 lux (
1 from 15 seconds after the start of color development using light with a color temperature of 5400K.
I kept applying it for 5 seconds.

The cyan coloring density of the resulting direct positive image was measured and the results are shown in Table 2.

Table 2 Samples using the compounds of the present invention have a large Dmax.
It was found that Dmin was small and favorable results were obtained.

Example 3 The following photographic material was prepared using Emulsion 1.

Paper support laminated on both sides with polyethylene (thickness 10
A color photographic light-sensitive material was prepared in which four layers of Strategist (from the next layer) were coated on the front side of the film (0 micron), and layers of Strategist 5 to Strategist 6 were coated on the back side. The polyethylene coating side of the first layer contains titanium white as a white pigment and a trace amount of ultramarine as a bluish dye.

(Photosensitive layer composition) The ingredients and coating amounts in g/' units are shown below.

Regarding silver halide, the coating amount is shown in terms of silver. The emulsion used in Section 3.4.6.11.12 was prepared according to the manufacturing method of Emulsion]. However, as the emulsion for the 14th layer, a Lippmann emulsion without surface chemical sensitization was used.

1st layer (antihalation layer) Black colloidal silver 0.10 Seratin 1.30 2nd layer (intermediate layer) Gelatin 0.70 3rd layer (low sensitivity red sensitive layer) Red sensitizing dye (ExS-1, 2, 3) Silver chlorobromide spectrally sensitized (average grain size 0.3 μm, octahedral)
0.06 red sensitizing dye (ExS-1,
Silver chlorobromide (average grain size 0) spectrally sensitized with
．． 45μm, octahedron) 0. 'IO
Gelatin 1.00 Cyan coupler (ExC-1,) 0111 Cyan coupler (ExC-2) 0.10 Antifading agent (Cpd-
2, 3, 4, 13 equivalents) 0, 12 Coupler dispersion medium (Cp d-5) 0. 03 coupler solvent (Solv-7, 2, 3 equivalent) (1,06 4th layer (high sensitivity red sensitive layer) Chlorobromide spectrally sensitized with red sensitizing dye (ExS-1, 2, 3) Silver (average particle size 0.60μm, octahedron)
0.14 gelatin
1.00 cyan coupler (l?, xC-],)
0. 15 cyan coupler (ExC-2)
0.15 Anti-fading agent (Cpd-2, 3, 4, 13 equivalents)
0, 15 Coupler dispersion medium (Cpd-5) 0.03 Kabrane medium (Solv-7, 2, 3 etc. N) 0, 10 5th layer (intermediate layer) Gelatin 1.00 Color mixing inhibitor (Cpd-7) 0.08 color mixing inhibitor solvent (
Solv-4,5 etc. M) 0,16 Polymer latex (Cpd-8) 0.10 6th layer (low sensitivity green sensitive layer) Silver chlorobromide spectrally sensitized with green sensitizing dye (ExS-3) (Average particle size 0.25μm, octahedron)
0.04 green sensitizing dye (Ex
Silver chlorobromide (average grain size 0) spectrally sensitized with
．． 45μm, octahedron) 0.
06 Gelatin 0.80 Magenta coupler (ExM-1,2 equivalent) 0,11 Anti-fading agent (Cpd-9) 0.10 Anti-stain agent (Cpd-10,22 equivalent) 0.014 Anti-stain agent (Cpd -23) 0.001 Stain inhibitor (Cpd-12) 0.01 Power puller dispersion medium (Cpd-5) 0.05 Coupler solvent (So
lv-4,6 equivalent) 0.15 7th layer (high-sensitivity green-sensitive layer) Emulsion 1 spectrally sensitized with a green sensitizing dye (Ex S-3,4) (average grain size 0.7 μm, octahedron)
0.1.0 gelatin
0.80 magenta coupler (BxM-1
,2) 0.10 Anti-fading agent (Cpd, -9) 0.1.0 Anti-stain agent (CI) d-10,22 etc.M) 0.013 Anti-stain agent (Cpd-23) 0.001 Anti-stain agent (Cpd-12>0.01 coupler dispersion medium (Cpd-5>0.05 coupler solvent (Sol
v-4,6 equivalent) 0.15 8th layer (intermediate layer) Same as 5th layer 9th layer (yellow filter layer) Yellow Colloy I/Silver 0.20 Gelatin 1.00 Color mixing prevention agent (Cpd
-7) 0.06 color mixing inhibitor solvent (Solv
-4,5 equivalent) 0.15 Polymer latex ((, pd-8) 0.10 10th layer (intermediate layer) Same as 5th layer 11th layer (low sensitivity blue sensitive layer) Blue sensitizing dye ( Silver chlorobromide spectrally sensitized with ExS-5,6), average grain size 0.45 μm, octahedral)
0.07 blue sensitizing dye (lK
Silver chlorobromide (average grain size 0.60 μm, octahedral) spectrally sensitized with xs-5,6) Gelatin yellow coupler (I-x Y-1,) stain inhibitor (Cpd-11) Anti-fade agent (Cpd-5) Coupler dispersion medium (Cpd-5) Coupler? Vehicle (Solv-2) 12th layer (high sensitivity blue sensitive layer) Blue sensitizing dye (ExS-5, 6) Silver bromide (average particle size 1, particle size distribution 21%, octahedral) Gelatin yellow coupler (EXY-1) Anti-stinting agent (Cpd-11) Anti-fading agent (Cpd-6) Coupler dispersion medium (Cpd-5) Coupler? Container (Solv-2) 13th layer (ultraviolet absorbing layer) Gelatin ultraviolet absorber < Cpd-I, 3, with spectral sensitization of 2 μm, condyle 0.25 1.00 0.41 0.00 0.10 0 .05 0.10 0,15 13 equivalents) 1,00 Color mixing inhibitor (cpd-6,14 equivalents) 0,06 Dispersion medium (Cpd-5) 0.05 Ultraviolet absorber solvent (Solv-1,2 Equivalent amount) 0, 15 Anti-irradiation dye (Cpa-15, 16 grade>
0.02 anti-irradiation dye (Cpd-17,188 eq.
0.02 14th layer (protective layer) Fine grain silver chlorobromide (silver chloride 97 mol%, average size 0.2
μm>0.05 Acrylic modified copolymer of polyvinyl alcohol (degree of modification 17%)
0.02 polymethyl methacrylate particles (average particle size 2.4 microns), silicon oxide (average particle size 5 μm) equivalent amount 0.05 gelatin
1.50 Ceratin hardening agent (+-1-1
) O, 1, 7 15th layer (back layer) Gelatin 2.50 16th layer (
Back protective layer) Polymethyl methacrylate-1/particles (average particle Reize 2)
．． 4 microns), silicon oxide (average particle size 5 microns) equivalent amount 0.05 geladine
2.00 gelatin hardener (H-1)
0.11 Each photosensitive layer contains E x Z K as a nucleating agent.
-1 was used in an amount of 10-3% by weight based on the amount of silver halide coated, and Cpd-24 was used in an amount of 10-2% by weight as a nucleation accelerator.

Furthermore, each layer contains alkanol XC (
DuPont) and sodium hyalkylhensensulponate, succinate ester and Ma as coating aids.
gefac F-120 (manufactured by Dainichi Ink Co., Ltd.) was used. (Cpd-19, 20, 21) was used as a stabilizer in the silver halide and colloidal silver containing layers. This sample was designated as sample number 301. The structural formulas of compounds used in Examples are shown.

F, x S XS 303+1 xS xS (CI+2)4 (C11□)4 xS SO,H・N(C2H,,),1 pd ■ xS pd pd pd C4I19(t) pd pd polyethyl acrylate pd +CH2 CH→-4 (n=100~I　000) CON HCa Hq (t) pd pd pd R pd pd 0 ■ pd pd H pd pa ■ 03K SO,K pd (CIl□)ISO! (C11□): +5OH1K pd pd δII pd pd p d ExC / ExY-2 ExC-2 α ExY / C3H1□(on ExY / C3I-1□7 (su So　　　　　　　　v　-/ ol ■　－－ Di(,2-ethelhexyl)phthalate root Trinonylphonufate 5olv-3di(3-methylhexyl)7talate tricresyl phosphate dibutyl phthalate trioctyl phosphate Di(,2-ethylhexyl)sebaque root /l,! -Binu (vinylnulfonyl) acetamido)ethane 7-(j-(j-mercaptotet lazol-7-yl)be/zami ]-70-Pro/g Lugil~/.

Ko, 3. Emulsion-13 was used in place of ≠-tetrahydroacridinium verchlorate emulsion No. 7Nj, and these samples were designated as Samples '#+30, 2, and 303, respectively.

Wedge exposure (7710 seconds 3000M
After giving s), the same treatment as in Example/ was performed.

Measure the degree of maze/color development of the obtained direct positive image - Hiroshi v-! 11-/ EXZK-/ S.

O 8゜ S.

established, The results were shown to a third person.

As shown in the third coating, it can be seen that the sample of the present invention has a high Dmax and a low result of 9ml.

[Effects of the present invention]

By forming an image using the direct positive photosensitive phase separation of the present invention, a direct positive image which has both a high maximum image density and a low minimum image density and is extremely suitable for practical use can be obtained.

[Brief explanation of drawings]

FIG. 7 shows the preferred half width of the X-ray diffraction profile of silver chlorobromide emulsion grains. The horizontal axis shows the molten chlorine in the silver chlorobromide grains, and the vertical axis shows the half width (Δ-θ0)-tag. Figure 1 shows an emulsion charging bag* (mixer and reaction vessel) used in the examples of the present invention.

Claims (1)

[Claims] A direct positive photographic light-sensitive material having at least one emulsion layer containing internal latent image type silver halide grains that have not been fogged in advance, wherein the internal latent image type silver halide grains contain 5 mol% or more of silver chloride; A direct positive photographic light-sensitive material characterized in that the distribution of silver chloride in at least some regions containing silver chloride in the grains is completely uniform.